CN102471186A - 制备芳基、杂芳基或烯基取代的不饱和烃类的方法 - Google Patents
制备芳基、杂芳基或烯基取代的不饱和烃类的方法 Download PDFInfo
- Publication number
- CN102471186A CN102471186A CN2010800360098A CN201080036009A CN102471186A CN 102471186 A CN102471186 A CN 102471186A CN 2010800360098 A CN2010800360098 A CN 2010800360098A CN 201080036009 A CN201080036009 A CN 201080036009A CN 102471186 A CN102471186 A CN 102471186A
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- Prior art keywords
- heteroaryl
- class
- aryl
- alkenyl
- group
- Prior art date
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- 125000001072 heteroaryl group Chemical group 0.000 title claims abstract description 45
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 31
- 229930195735 unsaturated hydrocarbon Natural products 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 61
- -1 heteroaryl halide Chemical class 0.000 claims abstract description 51
- 238000004821 distillation Methods 0.000 claims abstract description 32
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 150000001502 aryl halides Chemical class 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 125000003342 alkenyl group Chemical group 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 15
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- 239000012043 crude product Substances 0.000 abstract 2
- 125000005843 halogen group Chemical group 0.000 description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- IBXNCJKFFQIKKY-UHFFFAOYSA-N 1-pentyne Chemical compound CCCC#C IBXNCJKFFQIKKY-UHFFFAOYSA-N 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 7
- 239000003513 alkali Substances 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- VWWMOACCGFHMEV-UHFFFAOYSA-N dicarbide(2-) Chemical compound [C-]#[C-] VWWMOACCGFHMEV-UHFFFAOYSA-N 0.000 description 5
- 229950004394 ditiocarb Drugs 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000002390 heteroarenes Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 5
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 3
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 3
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- DEGIOKWPYFOHGH-UHFFFAOYSA-N pent-1-ynylbenzene Chemical compound CCCC#CC1=CC=CC=C1 DEGIOKWPYFOHGH-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 238000007341 Heck reaction Methods 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000000449 nitro group Chemical class [O-][N+](*)=O 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- JYYMLZLAIOASOM-UHFFFAOYSA-N (4-methylpiperazin-1-yl)-piperidin-4-ylmethanone;dihydrochloride Chemical compound Cl.Cl.C1CN(C)CCN1C(=O)C1CCNCC1 JYYMLZLAIOASOM-UHFFFAOYSA-N 0.000 description 1
- UDYXMTORTDACTG-UHFFFAOYSA-N 1,1,3-tributylthiourea Chemical compound CCCCNC(=S)N(CCCC)CCCC UDYXMTORTDACTG-UHFFFAOYSA-N 0.000 description 1
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 description 1
- RINOYHWVBUKAQE-UHFFFAOYSA-N 1-iodo-2-methylbenzene Chemical compound CC1=CC=CC=C1I RINOYHWVBUKAQE-UHFFFAOYSA-N 0.000 description 1
- GLULFBYVZPZFJQ-UHFFFAOYSA-N 1-prop-2-ynyl-2h-pyridine Chemical compound C#CCN1CC=CC=C1 GLULFBYVZPZFJQ-UHFFFAOYSA-N 0.000 description 1
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- OTTZHAVKAVGASB-HYXAFXHYSA-N 2-Heptene Chemical compound CCCC\C=C/C OTTZHAVKAVGASB-HYXAFXHYSA-N 0.000 description 1
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QNTARNCGFNQQRP-UHFFFAOYSA-N 5-carbamothioylsulfanylpentyl carbamodithioate Chemical compound NC(=S)SCCCCCSC(N)=S QNTARNCGFNQQRP-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HXKCUQDTMDYZJD-UHFFFAOYSA-N Methyl selenac Chemical compound CN(C)C(=S)S[Se](SC(=S)N(C)C)(SC(=S)N(C)C)SC(=S)N(C)C HXKCUQDTMDYZJD-UHFFFAOYSA-N 0.000 description 1
- VLCDUOXHFNUCKK-UHFFFAOYSA-N N,N'-Dimethylthiourea Chemical compound CNC(=S)NC VLCDUOXHFNUCKK-UHFFFAOYSA-N 0.000 description 1
- KFFQABQEJATQAT-UHFFFAOYSA-N N,N'-dibutylthiourea Chemical compound CCCCNC(=S)NCCCC KFFQABQEJATQAT-UHFFFAOYSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- KQJQICVXLJTWQD-UHFFFAOYSA-N N-Methylthiourea Chemical compound CNC(N)=S KQJQICVXLJTWQD-UHFFFAOYSA-N 0.000 description 1
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
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- QSHTUEAIYVDUDS-UHFFFAOYSA-N [Ca].CN(C(S)=S)C Chemical compound [Ca].CN(C(S)=S)C QSHTUEAIYVDUDS-UHFFFAOYSA-N 0.000 description 1
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000001584 benzyloxycarbonyl group Chemical group C(=O)(OCC1=CC=CC=C1)* 0.000 description 1
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- XTFSWQKNABTKAT-UHFFFAOYSA-L bis(diethylcarbamothioylsulfanyl)lead Chemical compound [Pb+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S XTFSWQKNABTKAT-UHFFFAOYSA-L 0.000 description 1
- USBHFGNOYVOTON-UHFFFAOYSA-K bis(dimethylcarbamothioylsulfanyl)bismuthanyl n,n-dimethylcarbamodithioate Chemical compound [Bi+3].CN(C)C([S-])=S.CN(C)C([S-])=S.CN(C)C([S-])=S USBHFGNOYVOTON-UHFFFAOYSA-K 0.000 description 1
- WRBHGAMSUYCQFW-UHFFFAOYSA-L bis(piperidine-1-carbothioylsulfanyl)lead Chemical compound [Pb+2].[S-]C(=S)N1CCCCC1.[S-]C(=S)N1CCCCC1 WRBHGAMSUYCQFW-UHFFFAOYSA-L 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
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- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical class NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
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- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000011097 chromatography purification Methods 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- OBBCYCYCTJQCCK-UHFFFAOYSA-L copper;n,n-diethylcarbamodithioate Chemical compound [Cu+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S OBBCYCYCTJQCCK-UHFFFAOYSA-L 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 description 1
- 125000003678 cyclohexadienyl group Chemical group C1(=CC=CCC1)* 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- JQVDAXLFBXTEQA-UHFFFAOYSA-O dibutylazanium Chemical compound CCCC[NH2+]CCCC JQVDAXLFBXTEQA-UHFFFAOYSA-O 0.000 description 1
- RLULIUSIDLLCSW-UHFFFAOYSA-N diethylcarbamothioylsulfanylselanyl n,n-diethylcarbamodithioate Chemical compound CCN(CC)C(=S)S[Se]SC(=S)N(CC)CC RLULIUSIDLLCSW-UHFFFAOYSA-N 0.000 description 1
- 229940116901 diethyldithiocarbamate Drugs 0.000 description 1
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- ILXWFJOFKUNZJA-UHFFFAOYSA-N ethyltellanylethane Chemical group CC[Te]CC ILXWFJOFKUNZJA-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- QLNAVQRIWDRPHA-UHFFFAOYSA-N iminophosphane Chemical compound P=N QLNAVQRIWDRPHA-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 125000005905 mesyloxy group Chemical group 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QGTHALAWFUFVCU-UHFFFAOYSA-L n,n-dimethylcarbamodithioate;lead(2+) Chemical compound [Pb+2].CN(C)C([S-])=S.CN(C)C([S-])=S QGTHALAWFUFVCU-UHFFFAOYSA-L 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- IBGCXOFOCKCBNQ-UHFFFAOYSA-N nitro cyanate Chemical group [O-][N+](=O)OC#N IBGCXOFOCKCBNQ-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
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- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- HUMLQUKVJARKRN-UHFFFAOYSA-M sodium;n,n-dibutylcarbamodithioate Chemical compound [Na+].CCCCN(C([S-])=S)CCCC HUMLQUKVJARKRN-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000005420 sulfonamido group Chemical group S(=O)(=O)(N*)* 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
- AUMBZPPBWALQRO-UHFFFAOYSA-L zinc;n,n-dibenzylcarbamodithioate Chemical compound [Zn+2].C=1C=CC=CC=1CN(C(=S)[S-])CC1=CC=CC=C1.C=1C=CC=CC=1CN(C(=S)[S-])CC1=CC=CC=C1 AUMBZPPBWALQRO-UHFFFAOYSA-L 0.000 description 1
- KMNUDJAXRXUZQS-UHFFFAOYSA-L zinc;n-ethyl-n-phenylcarbamodithioate Chemical compound [Zn+2].CCN(C([S-])=S)C1=CC=CC=C1.CCN(C([S-])=S)C1=CC=CC=C1 KMNUDJAXRXUZQS-UHFFFAOYSA-L 0.000 description 1
- NCSQKSMOKBZEDF-UHFFFAOYSA-L zinc;n-methyl-n-phenylcarbamodithioate Chemical compound [Zn+2].[S-]C(=S)N(C)C1=CC=CC=C1.[S-]C(=S)N(C)C1=CC=CC=C1 NCSQKSMOKBZEDF-UHFFFAOYSA-L 0.000 description 1
- YBKBEKGVHFHCRI-UHFFFAOYSA-L zinc;piperidine-1-carbodithioate Chemical compound [Zn+2].[S-]C(=S)N1CCCCC1.[S-]C(=S)N1CCCCC1 YBKBEKGVHFHCRI-UHFFFAOYSA-L 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
Classifications
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Abstract
本发明涉及一种制备芳基、杂芳基或烯基取代的不饱和烃类的方法,包括:在钯催化剂的存在下,使芳基卤化物类、杂芳基卤化物类或烯基卤化物类与炔烃类或烯烃类发生反应以获得粗生成物,接下来,在具有至少一个NC=S基团的化合物存在下,对所述粗生成物进行蒸馏纯化。
Description
技术领域
本发明涉及通过使用钯催化剂使芳基卤化物类、杂芳基卤化物类或烯基卤化物类与炔烃类或烯烃类发生偶联反应,从而在工业上高产率地制备芳基、杂芳基或烯基取代的不饱和烃类的方法。
背景技术
芳基、杂芳基或烯基取代的不饱和烃类可用作生理活性物质(医药、农药等)或功能材料(液晶材料、电子材料、光学材料、照相用添加剂、热固化性树脂等)或者它们的合成中间体(例如,参见专利文献6~9)。
芳基或烯基取代的不饱和烃类(例如)是这样得到的:通过在钯催化剂存在下使芳基卤化物类或烯基卤化物类与炔烃类或烯烃类反应(所谓的薗头偶联(Sonogashira coupling)或沟吕木-赫克反应(Mizoroki-Heck reaction))。
关于通过薗头偶联来制备芳基或烯基取代的不饱和烃类的方法,已经提出了多种方案。例如,专利文献1中公开了一种制备芳香族乙炔化合物的方法:在钯催化剂、铜盐、碱以及能够释放出卤素离子的化合物的存在下,使芳香族卤化物与乙炔化合物反应,接着加入稀盐酸和有机溶剂以进行分液,并通过硅胶柱色谱纯化有机相,从而制备芳香族乙炔化合物。
专利文献2中公开了一种制备偶联反应产物的方法:在含有钯等过渡金属元素、无机盐、以及配体(如,三芳基膦或亚氨基膦化合物等)的催化剂存在下,使末端具有次甲基的烯烃类与具有卤素基团等离去基团的有机化合物发生偶联反应,接着采用制备用高速液相色谱从该反应混合物中分离生成物,并采用凝胶渗透色谱对生成物进行纯化,从而得到作为目的物的偶联反应产物。
在专利文献1和2所记载的制备方法中,虽然采用萃取和色谱法纯化,但是色谱法不合适大量生产。
专利文献3中公开了一种苯基炔类的制备方法,包括以下步骤:在胺溶剂、钯络合物催化剂以及铜盐的存在下,使卤代苯酚和乙炔化合物反应,向得到的反应混合物中加入稀盐酸进行分液,并除去氯化氢,接下来加入能够与钯和铜形成络合物的氨基化合物,并除去所生成的钯络合物和铜络合物。另外,专利文献5公开了一种合成具有含氮芳香族基团的乙炔化合物的方法:在钯催化剂、铜催化剂的存在下使乙炔基吡啶类与卤代芳基类反应。在专利文献3和专利文献5所记载的制备方法中,采用萃取以进行纯化。
在专利文献4中公开了一种制备芳基炔化合物的方法:在钯催化剂、碱和铜(Ⅰ)盐的存在下,使碘代甲苯等芳基卤化物与含氨基的乙炔化合物(如,N-(2-丙炔基)吡啶)反应,接下来减压除去溶剂,洗涤残留物,最后蒸馏纯化。在专利文献4记载的制备方法中,采用了蒸馏以进行纯化。
现有技术文献
专利文献
专利文献1:日本特开平10-114691号公报
专利文献2:日本特开2005-254092号公报
专利文献3:美国专利4540833号
专利文献4:日本特表2005-500392号公报
专利文献5:日本特开2006-248943号公报
专利文献6:WO 2003/018538
专利文献7:日本特开平5-25163号公报
专利文献8:日本特开平5-39250号公报
专利文献9:日本特开平4-225952号公报
发明内容
发明要解决的课题
作为工业上分离纯化生成物的方法,蒸馏是非常有效的方法。如专利文献4中记载的制备方法,对芳基卤化物类、杂芳基卤化物类或烯基卤化物类与炔烃类或烯烃类的偶联反应生成物进行蒸馏纯化,这适用于工业上的大规模生产。根据本发明人的研究,在小规模下进行蒸馏纯化,能够以高产率获得芳基、杂芳基或烯基取代的不饱和烃类。然而,当在相当于工业生产的大规模下进行蒸馏纯化时,芳基、杂芳基或烯基取代的不饱和烃类的产率有时大幅降低。
本发明的目的在于提供一种通过使用钯催化剂使芳基卤化物类、杂芳基卤化物类或烯基卤化物类与炔烃类或烯烃类发生偶联反应,从而即使在工业上的大规模生产中,也能够以高产率制备芳基、杂芳基或烯基取代的不饱和烃类(即,芳基炔烃类、芳基烯烃类、杂芳基炔烃类、杂芳基烯烃类、烯基炔烃类或烯基烯烃类)的方法。
解决课题的手段
本发明人为了实现上述目的进行了深入研究,结果发现,与小规模生产中的蒸馏纯化相比,在大规模生产的蒸馏纯化中,生成物在高温下被长时间加热,因而,当在该加热状态下有钯催化剂或其分解物残留时,偶联反应生成物发生分解。
然后,本发明人发现,当在二乙基二硫代氨基甲酸钠的存在下进行蒸馏纯化时,生成物的分解被抑制,并且产率的下降得到抑制。另外,本发明人发现,不仅是二乙基二硫代氨基甲酸钠,而且即使其一般化的具有至少一个NC=S基团的化合物,也能够抑制产率下降。本发明基于上述发现而完成。
即,本发明涉及这样一种芳基、杂芳基或烯基取代的不饱和烃类的制备方法:在钯催化剂的存在下,使芳基卤化物类、杂芳基卤化物类或烯基卤化物类与炔烃类或烯烃类发生反应,从而获得粗生成物,接下来,在具有至少一个NC=S基团的化合物存在下,对所述粗生成物进行蒸馏纯化。
发明效果
根据本发明,通过采用钯催化剂使芳基卤化物类、杂芳基卤化物类或烯基卤化物类与炔烃类或烯烃类发生偶联反应,即使在工业上的大规模生产中,也能够以高产率制备芳基、杂芳基或烯基取代的不饱和烃类。
获得这种效果的理由尚不确定,但可以推定如下。已知的是具有至少一个NC=S基团的化合物(如,二硫代氨基甲酸盐类和硫脲类等)与钯配位以形成不溶于溶剂的钯络合物(美国专利7300639号)。由此可以认为,来源于钯催化剂或其分解物(其是在进行了蒸馏纯化的生成物溶液中残留的钯催化剂或其分解物)的钯通过具有至少一个NC=S基团的化合物而变成不溶于溶剂的钯络合物,因此钯的反应活性下降,即使在高温下长时间被加热,生成物也不再进行分解反应。
具体实施方式
本发明的芳基、杂芳基或烯基取代的不饱和烃类的制备方法包括:在钯催化剂的存在下使芳基卤化物类、杂芳基卤化物类或烯基卤化物类与炔烃类或烯烃类反应,从而得到粗生成物,接下来,在具有至少一个NC=S基团的化合物存在下,对所述粗生成物进行蒸馏纯化。
本发明中所用的芳基卤化物类及杂芳基卤化物类是被至少一个卤素原子(离去基团)取代的芳香族化合物和杂芳香族化合物。这里,芳香族化合物和杂芳香族化合物是具有环的化合物,该环具有(4n+2)(其中n表示自然数)个π电子。因此,芳香族化合物包括苯、萘等。杂芳香族化合物是具有包含选自氮原子、硫原子、氧原子等杂原子的芳香族环的化合物,即,杂芳香族化合物包括吡啶、嘧啶、吡咯、吲哚、噻吩、呋喃等。芳基卤化物类和杂芳基卤化物类优选是其中至少一个卤素原子(离去基团)与sp2碳结合的芳香族化合物和杂芳香族化合物。
本发明中所用的烯基卤化物类为其中至少一个卤素原子(离去基团)与sp2碳结合的烯烃化合物。无卤素取代的烯烃化合物(例如)包括乙烯、丙烯、1-丁烯、2-丁烯、1-庚烯、2-庚烯、环己烯等。
作为卤素原子,可以举出氟原子、氯原子、溴原子和碘原子。关于取代的卤素原子,原子量越大,对于偶联反应的活性越高。例如,在3个氟原子和1个氯原子所取代的芳香族化合物中,氯原子部分易于发生偶联反应。
本发明中所用的芳基卤化物类、杂芳基卤化物类或烯基卤化物类还可以具有除卤素原子以外的取代基。
作为除卤素原子以外的取代基,可以举出甲基、乙基等烷基;苯基、萘基等芳基;氰基;羧基;甲氧羰基等烷氧羰基;苯氧羰基等芳氧基羰基;氨基甲酰基;N-苯基氨基甲酰基、N,N-二甲基氨基甲酰基等取代的氨基甲酰基;乙酰基等烷基羰基;苯甲酰基等芳基羰基;硝基;氨基;二甲氨基、苯胺基等取代的氨基;乙酰胺基、乙氧羰基氨基等酰氨基;甲磺酰氨基等磺酰氨基;琥珀酰亚氨基、苯二酰亚氨基等酰亚氨基;苯亚甲氨基等亚氨基;羟基;甲氧基等烷氧基;苯氧基等芳氧基;乙酰氧基等酰氧基;甲磺酰氧基等烷基磺酰氧基;苯磺酰氧基等芳基磺酰氧基;磺基;氨磺酰基;N-苯基氨磺酰基等取代的氨磺酰基;甲硫基等烷硫基;苯硫基等芳硫基;甲磺酰基等烷基磺酰基;以及苯磺酰基等芳基磺酰基,等。
当结合吸电子取代基作为除卤素原子以外的取代基时,偶联反应性大幅提高。作为吸电子取代基,可以举出:与进行偶联反应的卤素原子不同的其它卤素原子、氰基、烷氧羰基、芳氧羰基、取代或未取代的氨基甲酰基、烷基羰基、芳羰基、硝基、取代或未取代的氨磺酰基、烷基磺酰基和芳基磺酰基等。
本发明中使用的炔烃类为具有sp碳的化合物。例如,可以举出末端具有次甲基的化合物(例如,可以用式Ⅰ:R1C≡CH(式中,R1表示有机基团或氢原子)表示)、以及具有被锌或锡等金属取代的末端次甲基的有机金属化合物(例如,可以用式Ⅱ:R1C≡CM(式中,R1表示有机基团或氢原子,M表示含金属元素的基团)表示)。其中,本发明的制备方法优选适用于在炔键的α位具有氢原子的炔烃类。
本发明使用的烯烃类为具有sp2碳的化合物。作为所述烯烃类,例如,可以举出末端具有乙烯基的化合物(例如,可以用式Ⅲ:R1 2C=CH2(式中,两个R1各自独立地表示有机基团或氢原子)表示)。具体而言,包括乙烯、丙烯、1-丁烯、1-庚烯和1-己烯等。在沟吕木-赫克反应中,优选使用末端具有乙烯基的化合物。
在前述式Ⅰ、式Ⅱ和式Ⅲ中,作为由R1表示的有机基团,可以举出:烷基(甲基、乙基、丙基、丁基、叔丁基等)、烯基(乙烯基、丙烯基、烯丙基、丁烯基等)等脂肪族烃基;环烷基(环己基、环辛基等)、环烯基(环己烯基等)、环烷二烯基(环己二烯基等)、环烷基烷基(环己基甲基等)、环烯基烷基(环己烯基甲基等)、环烷二烯基烷基(环己二烯基甲基等)等脂环烃基;芳基(苯基、萘基等)、芳烷基(苄基、苯乙基等)等芳香族烃基。这些烃基可以在分子中具有双键或三键等不饱和键,或可以具有杂原子(O、N、S、P、Sn、B、Si原子等)。
另外,前述烃基可以具有羟基、烷氧基、芳氧基、酰基、羧基、烷氧羰基、芳氧羰基、氨基、N-取代氨基、硝基、氰基、卤素原子等取代基。
在式Ⅱ中,作为由M表示的含金属元素的基团,可以举出氯锌(ClZn-)、三甲基锡((CH3)3Sn-)和三丁基锡((C4H9)3Sn-)等。
在芳基卤化物类、杂芳基卤化物类或烯基卤化物类与炔烃类或烯烃类的偶联反应中,相对于芳基卤化物类、杂芳基卤化物类或烯基卤化物类中的每摩尔离去基团,炔烃类中的甲基或被金属取代的末端次甲基或者烯烃类中的乙烯基的使用比例优选为0.7摩尔~1.3摩尔。
作为钯催化剂,可以使用在薗头偶联或沟吕木-赫克反应中所用的公知的催化剂。例如,可以使用0价或2价的钯金属或其盐(包括络合物)等钯化合物。钯催化剂可以担载在活性炭等载体上。作为优选使用的钯催化剂,可以举出:钯(0)/碳、醋酸钯(Ⅱ)、氯化钯(Ⅱ)、乙酰丙酮钯(Ⅱ)、双(三苯基膦)合氯化钯(Ⅱ)、三(二亚苄基丙酮)二钯(0)、四(三苯基膦)钯(0)、PdCl2(PPh3)2和Pd(OAc)2·(PPh3)2等(在此,Ph表示苯基、OAc表示乙酰氧基)。其中特别优选使用四(三苯基膦)钯(0)。相对于1摩尔的芳基卤化物类、杂芳基卤化物类或烯基卤化物类,钯催化剂优选使用0.001毫摩尔~1摩尔,更优选使用0.01毫摩尔~0.01摩尔,特别优选使用0.01毫摩尔~0.05摩尔。
在本发明中,可以将1价或2价的铜盐、优选1价的铜盐与钯催化剂一起使用。在铜盐中,优选氯化铜(Ⅰ)。相对于1摩尔的芳基卤化物类、杂芳基卤化物类或烯基卤化物类,铜盐的使用量优选为0.1毫摩尔~0.1摩尔。
在本发明中,还可以在加入钯催化剂的同时一同加入膦基配体来进行反应。作为膦基配体,可以举出三芳基膦、二芳基烷基膦、芳基二烷基膦、三烷基膦、亚氨基膦等。其中,优选三苯基膦。另外,可以使用在分子中具有两个磷原子的双齿配体。相对于1摩尔的芳基卤化物类、杂芳基卤化物类或烯基卤化物类,膦基配体的使用量优选为0.1毫摩尔~0.1摩尔。
在本发明中,优选进一步加入碱以进行反应。作为碱,可以使用氢氧化钠、碳酸钠、碳酸氢钠、氢氧化钾、碳酸钾、碳酸氢钾、氢化钠、甲醇钠、乙醇钠、叔丁醇钠、叔丁醇钾等,以及作为有机碱的三乙胺、二乙胺、哌啶、吡咯烷、1,8-二氮杂双环[5.4.0]-7-十一碳烯(DBU)和吡啶等。其中,优选有机碱,特别优选三乙胺和二乙胺。相对于1摩尔的芳基卤化物类、杂芳基卤化物类或烯基卤化物类,碱的使用量优选为1摩尔~100摩尔,更优选1摩尔~10摩尔。碱可以捕获副产物卤化氢。
作为反应溶剂,通常使用有机溶剂。作为优选的反应溶剂,可以使用甲苯等芳香烃类溶剂;乙腈、N,N-二甲基乙酰胺和N,N-二甲基甲酰胺等酰胺类溶剂;四氢呋喃等醚类溶剂;以及吡啶等。其中,优选使用溶解性良好的酰胺类溶剂。在炔烃类或烯烃类以及芳基卤化物类、杂芳基卤化物类或烯基卤化物类的溶解性差的情况下,可以加入作为助溶剂的四氢呋喃等而形成混合溶剂。
偶联反应时的温度通常为0℃~150℃,优选20℃~130℃,更优选20℃~110℃。反应可以在空气氛围下进行,但通常优选在惰性气体氛围下进行。作为惰性气体,可以举出氩气、氦气等稀有气体;以及氮气等。反应时的压力可以根据芳基卤化物类、杂芳基卤化物类或烯基卤化物类以及炔烃类或烯烃类的种类进行合适地选择,但压力通常为0.0001MPa~100MPa,优选0.001MPa~10MPa,更优选0.01MPa~1MPa。
在本发明中,在对上述偶联反应中所获得的粗生成物进行蒸馏纯化之前可以进行溶剂萃取。对萃取条件没有特别限定,只要可以除去催化剂等杂质即可。例如,首先向偶联反应中得到的粗生成物中加入稀盐酸(氯化氢的水溶液)等酸和甲基环己烷等有机溶剂以进行萃取。向通过上述萃取得到的有机相中加水以进行萃取。向通过上述萃取得到的有机相中加入碳酸氢钠水溶液或氨水等碱以进行萃取。向通过上述萃取得到的有机相中加入氯化钠水溶液以进一步进行萃取。最后,从通过上述萃取得到的有机相中蒸发溶剂,从而将浓度调整为适于进行蒸馏纯化。
在本发明中,将在上述偶联反应中得到的粗生成物或者对该粗生成物进行溶剂萃取处理而得到的粗生成物蒸馏纯化。该蒸馏纯化需要在具有至少一个NC=S基团的化合物存在下进行。另外,通过在高温下加热进行的浓缩也优选在具有至少一个NC=S基团的化合物存在下进行。
作为具有至少一个NC=S基的化合物,可以举出二硫代氨基甲酸及其盐、硫脲类、硫代氨基甲酸O-烷基酯类、一硫化四烷基秋兰姆类、二硫化四烷基秋兰姆类等。其中,优选二硫代氨基甲酸盐及硫脲类。
作为二硫代氨基甲酸盐,可以举出:二甲基二硫代氨基甲酸锌、二甲基二硫代氨基甲酸钠、二甲基二硫代氨基甲酸铋、二甲基二硫代氨基甲酸钙、二甲基二硫代氨基甲酸铜、二甲基二硫代氨基甲酸铅、二甲基二硫代氨基甲酸硒、二乙基二硫代氨基甲酸钠、二乙基二硫代氨基甲酸铵、二乙基二硫代氨基甲酸铜、二乙基二硫代氨基甲酸铅、二乙基二硫代氨基甲酸硒、二乙基二硫代氨基甲酸碲、二丁基二硫代氨基甲酸锌、二丁基二硫代氨基甲酸钠、二丁基二硫代氨基甲酸二丁基铵、二苄基二硫代氨基甲酸锌、甲基苯基二硫代氨基甲酸锌、乙基苯基二硫代氨基甲酸锌、五亚甲基二硫代氨基甲酸锌、五亚甲基二硫代氨基甲酸钙、五亚甲基二硫代氨基甲酸铅、五亚甲基二硫代氨基甲酸钠、五亚甲基二硫代氨基甲酸哌啶等。作为二硫代氨基甲酸盐,优选钠盐。
作为硫脲类,可以举出:硫脲、1,3-二甲基硫脲、1,3-二乙基-2-硫脲、1-乙酰基-2-硫脲、1-烯丙基-3-(2-羟乙基)-2-硫脲、1-脒基-2-硫脲、1,3-二乙基硫脲、1,3-二苯基硫脲、1,3-二丁基硫脲、1,3-二甲基硫脲、三丁基硫脲、三甲基硫脲、1,3-双(二甲氨基丙基)-2-硫脲、四甲基硫脲和N-甲基硫脲等。
相对于蒸馏前的粗生成物中所含的芳基、杂芳基或烯基取代的不饱和烃类,具有至少一个NC=S基团的化合物的使用量优选为0.1摩尔%~2摩尔%、更优选0.2摩尔%~0.5摩尔%。当具有至少一个NC=S基团的化合物的量过少时,芳基、杂芳基或烯基取代的不饱和烃类的产率往往下降。当具有至少一个NC=S基团的化合物的量过多时,使用通过蒸馏纯化得到的芳基、杂芳基或烯基取代的不饱和烃类作为原料的还原反应(氢化反应)或环化反应等的进行往往被抑制。
对蒸馏方法没有特别限定,但本发明中优选减压蒸馏。通过减压蒸馏,可以在抑制芳基、杂芳基或烯基取代的不饱和烃类过热的同时,促进蒸发。
对能够适于本发明的蒸馏装置没有特别限定。例如,可以举出简单蒸馏装置、层板塔、填充塔等。蒸馏温度和蒸馏时间可根据在上述反应中得到的芳基、杂芳基或烯基取代的不饱和烃类的沸点、所添加的具有至少一个NC=S基团的化合物的沸点、以及溶剂的沸点等合适地确定。
实施例
下面示出实施例和对比例,并通过它们对本发明进行具体说明,但本发明并不限于这些实施例。此外,除非另外指明,“份”和“%”以质量为基准。
另外,在下面的实施例和对比例中,粗生成物中的目的物浓度通过HPLC分析来确定。
HPLC分析条件
柱子:Waters Symmetry C18 5μm 4.6×150mm
温度:50℃
流速:1mL/min
波长:245nm
流动相组成:MeCN∶H2O∶10%H3PO4=550∶450∶1
内标物:二苯甲酮
另外,目的物的鉴定通过H1-NMR分析来进行。
实施例1:
将82.43g溴代苯装入反应器中,并向其中加入250ml的N,N-二甲基甲酰胺和84.7g三乙胺。用氮气置换反应器内部。
加入2.3g四(三苯基膦)钯和1g氯化铜(Ⅰ),并将温度提高至100℃。在保持100℃的情况下,在2小时内滴加34.06g 1-戊炔。滴加完成后,在保持温度为100℃的同时进一步搅拌2小时。将所得溶液冷却至室温,向溶液中加入335ml的10%盐酸,并搅拌30分钟。之后用甲基环己烷萃取。向获得的有机相中加水以进行萃取。向获得的有机相中加入4%的碳酸氢钠水溶液以进行萃取。接下来向获得的有机相中加入10%的氯化钠水溶液以进行萃取。最后,从获得的有机相中蒸馏除去溶剂,得到粗生成物(Ⅰ)。
将前述获得的粗生成物(Ⅰ)和N,N-二乙基二硫代氨基甲酸钠三水合物(相对于粗生成物(Ⅰ)中所含的1-苯基-1-戊炔,N,N-二乙基二硫代氨基甲酸钠三水合物的比例为1摩尔%)放入到配备有回流器的烧瓶中,升温至160℃,并在160℃下常压加热120分钟。将该液体冷却至室温,接下来在温度约为96℃、压力为1.0mmHg下进行减压蒸馏。1-苯基-1-戊炔的产率为64.9%。
对比例1
按照与实施例1相同的方式获得粗生成物(Ⅰ)。将该粗生成物(Ⅰ)放入到配备有回流器的烧瓶中,升温至160℃,并在160℃下常压加热120分钟。将该液体冷却至室温,接下来在温度约为96℃、压力为1.0mmHg下进行减压蒸馏。1-苯基-1-戊炔的产率为50.3%。
实施例2
按照与实施例1相同的方式获得粗生成物(Ⅱ),不同之处在于,将34.06g的1-戊炔替换为42.06g的1-戊炔-3-醇,并且按照与实施例1相同的方式对粗生成物(Ⅱ)进行加热和蒸馏。1-苯基-1-戊炔-3-醇的产率为58.0%。
对比例2
按照与实施例1相同的方式获得粗生成物(Ⅱ),不同之处在于,将34.06g的1-戊炔替换为42.06g的1-戊炔-3-醇,并且按照与对比例1相同的方式对粗生成物(Ⅱ)进行加热和蒸馏。1-苯基-1-戊炔-3-醇的产率为10.9%。
实施例3
按照与实施例1相同的方式获得粗生成物(Ⅲ),不同之处在于,将34.06g的1-戊炔替换为42.06g的1-戊炔-4-醇,并且按照与实施例1相同的方式对粗生成物(Ⅲ)进行加热和蒸馏。1-苯基-1-戊炔-4-醇的产率为63.2%。
对比例3
按照与实施例1相同的方式获得粗生成物(Ⅲ),不同之处在于,将34.06g的1-戊炔替换为42.06g的1-戊炔-4-醇,并且按照与对比例1相同的方式对粗生成物(Ⅲ)进行加热和蒸馏。1-苯基-1-戊炔-4-醇的产率为10.0%。
实施例4
按照与实施例1相同的方式获得粗生成物(Ⅳ),不同之处在于,将34.06g的1-戊炔替换为42.06g的2-甲基-3-丁炔-2-醇,并且按照与实施例1相同的方式对粗生成物(Ⅳ)进行加热和蒸馏。1-苯基-3-甲基-1-丁炔-3-醇的产率为57.2%。
对比例4
按照与实施例1相同的方式获得粗生成物(Ⅳ),不同之处在于,将34.06g的1-戊炔替换为42.06g的2-甲基-3-丁炔-2-醇,并且按照与对比例1相同的方式对粗生成物(Ⅳ)进行加热和蒸馏。1-苯基-3-甲基-1-丁炔-3-醇的产率为53.8%。
如上所述,可以看出,在向芳基卤化物类、杂芳基卤化物类或烯基卤化物类与炔烃类或烯烃类的偶联反应产物中加入二硫代氨基甲酸盐或硫脲类等具有至少一个NC=S基团的化合物的情况中,即使通过常压加热加入了额外的热量并且之后进行蒸馏纯化,偶联反应产物也不会分解而是保留下来,因此产率高。另一方面,在不加入具有NC=S基团的化合物的情况中,由于常压加热以及蒸馏纯化中的热量,偶联反应产物发生分解,因此产率下降。
尽管已经参照特定实施方案详细描述了本发明,但对于本领域人员显而易见的是,可以在不脱离本发明精神和范围的情况下,进行各种变更和修改。
本申请基于2009年8月18日提交的日本专利申请2009-188859,其内容以引用方式并入本文。
Claims (5)
1.一种制备芳基、杂芳基或烯基取代的不饱和烃类的方法,包括:
在钯催化剂的存在下,使芳基卤化物类、杂芳基卤化物类或烯基卤化物类与炔烃类或烯烃类发生反应,从而获得粗生成物,
接下来,在具有至少一个NC=S基团的化合物存在下,对所述粗生成物进行蒸馏纯化。
2.根据权利要求1所述的制备芳基、杂芳基或烯基取代的不饱和烃类的方法,其中所述具有至少一个NC=S基团的化合物为二硫代氨基甲酸盐或硫脲类。
3.根据权利要求1或2所述的制备芳基、杂芳基或烯基取代的不饱和烃类的方法,其中在所述芳基卤化物类、杂芳基卤化物类或烯基卤化物类与所述炔烃类或烯烃类反应之后、并且在所述蒸馏纯化之前,进行溶剂萃取。
4.根据权利要求1至3中任意一项所述的制备芳基、杂芳基或烯基取代的不饱和烃类的方法,其中,相对于蒸馏前的粗生成物中所含的芳基、杂芳基或烯基取代的不饱和烃类,所述具有至少一个NC=S基团的化合物的用量为0.1摩尔%~2摩尔%。
5.根据权利要求1至3中任意一项所述的制备芳基、杂芳基或烯基取代的不饱和烃类的方法,其中,相对于蒸馏前的粗生成物中所含的芳基、杂芳基或烯基取代的不饱和烃类,所述具有至少一个NC=S基团的化合物的用量为0.2摩尔%~0.5摩尔%。
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